Polymeric materials

ABSTRACT

Monomers having the structure and a polymer comprising as part of its polymer backbone a moiety of Formula (II): 
                         
where one of R 6  to R 10  represents A-O— and one of R 6  to R 10  represents —O—B and the remainder of R 6  to R 10  represent H, where A and B represent the remainder of the polymer backbone and may be the same or different. The monomers are diol, dicarboxylic acid, epoxy, and succinate compounds containing a cineole structure wherein a compound for use in preparation of polymer, the compound selected from

RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 13/513,524, filedJun. 1, 2012, which is a §371 national stage of PCT InternationalApplication No. PCT/AU2010/001628, filed Dec. 2, 2010, which claims thepriority of Australian Provisional Application No. 2009905928, filedDec. 4, 2009, the contents of each of which are hereby incorporated byreference in their entirety into this application.

FIELD OF THE INVENTION

The present invention relates to polymeric materials, and in particularto polymeric materials prepared using a cyclic compound derived from arenewable source.

BACKGROUND OF THE INVENTION

There is a continuing demand for new polymeric materials with new anduseful properties. The majority of synthetic polymers are formed fromthe polymerisation of compounds derived from the petroleum industry. Thevolatile price of oil, combined with its non-renewable nature, has ledto a considerable amount of research effort being directed towardsdiscovering alternate sources of compounds for use in polymer synthesis.One such source that has received continuing interest is biologicallyderived material that can function as, or be converted into,industrially useful compounds for use in polymer synthesis. Therenewable nature of many biologically derived materials makes themparticularly attractive.

Unfortunately, however, many biologically derived materials do notpossess properties that would otherwise make them suitable compounds forpolymer synthesis. For example many biologically derived materials, suchas unsaturated vegetable oils, typically do not possess usefulfunctionality (such as amino, hydroxyl, carboxy groups and suitablyreactive double bonds) that readily allow for polymerisation to takeplace. In the course of synthetically installing such usefulfunctionality, through oxidation of one or more double bonds to formhydroxyl groups for example, the mechanical properties of thebiologically derived materials are often adversely modified. On theother hand, some biologically derived materials may possess usefulfunctionality for polymerisation but may not possess other structuralfeatures providing desirable properties for new and useful polymericmaterials.

An opportunity therefore exists to provide polymers with new and usefulproperties which have been prepared using compounds derived from arenewable source.

SUMMARY OF THE INVENTION

It has now been found that a particular class of cyclic compound ofFormula (I) can advantageously be used in the preparation of polymericmaterials:

where one of R¹ to R⁵ represents X—O—, one of R¹ to R⁵ represents —O—Y,and the remainder of R¹ to R⁵ represent H, where X and Y may be the sameor different and represent H or a group comprising reactivefunctionality. In some embodiments, X and Y may be independentlyselected from H and optionally substituted hydroxyalkyl, hydroxyalkylcarbonyl, aminoalkyl, aminoalkylcarbonyl, carboxyalkyl,carboxyalkylcarbonyl, epoxyalkyl and unsaturated variants thereof suchas aminoalkylene. In one embodiment X and Y are each H.

Compounds of Formula (I) can advantageously be derived from a number ofnaturally occurring or semi-synthetic sources including α-pincnc andsobrcrol, which in turn may be sourced from a range of renewable plantsources such as pine, bay, tea tree, mugwort, sweet basil, wormwood,rosemary, sage and Eucalyptus.

In one aspect, the invention therefore provides a polymer comprising aspart of its polymer backbone a moiety of Formula (II):

where one of R⁶ to R¹⁰ represents A-O—, one of R⁶ to R¹⁰ represents—O—B, and the remainder of R⁶ to R¹⁰ represent H, where A and Brepresent the remainder of the polymer backbone and may be the same ordifferent.

In a further aspect, the present invention provides a product (such as asheet, fibre or film) comprising the polymer of the invention.

In another aspect, the present invention provides a polymer blendcomprising the polymer of the invention and at least one other polymer.In some embodiments the polymer blend may be a physical blend. In someembodiments the polymer blend may be a melt mixed blend.

In yet a further aspect, the present invention provides for use of acompound of Formula (I) in the preparation or modification of polymer:

where one of R¹ to R⁵ represents X—O—, one of R¹ to R⁵ represents —O—Y,and the remainder of R¹ to R⁵ represent H, where X and Y may be the sameor different and represent H or a group comprising functionality whichis capable of reacting with one or more monomers and/or with one or morepolymers.

By a compound of Formula (I) being used in the “preparation” of polymeris meant that the compound of Formula (I) reacts with one or moremonomers to form polymer covalently incorporating the reacted residue ofthe compound of Formula (I).

By a compound of Formula (I) being used in the modification of polymeris meant that the compound of Formula (I) reacts with one or morepolymers and becomes covalently coupled thereto.

By a compound of Formula (I) being “capable of reacting with one or moremonomers or one or more polymers” is meant that the compound of Formula(I) and the one or more monomers and/or the one or more polymers willhave compatible chemical functionality that can undergo reaction. Forexample, polymer may be prepared by functional groups of the compound ofFormula (I) reacting with functional groups of one or more monomers(e.g. via a polymerisation reaction). As a further example, polymer maybe modified by functional groups of the compound of Formula (I) reactingwith functional groups of the one or more polymers that is to bemodified. Such reactions may be promoted by any suitable means, forexample by melt mixing the components or by combining the components ina suitable solvent.

In a further aspect, the invention provides a process for preparingpolymer or modifying polymer, the process comprising reacting a compoundof Formula (I):

with monomer and/or polymer, where one of R¹ to R⁵ represents X—O— andone of R¹ to R⁵ represents —O—Y and the remainder of R¹ to R⁵ representH, where X and Y may be the same or different and represent H or a groupcomprising functionality which is capable of reacting with the monomerand polymer.

By a compound of Formula (I) “reacting” with monomer and/or polymer ismeant that the compound of Formula (I) reacts with and becomescovalently coupled to the monomer and/or polymer.

By a compound of Formula (I) being “capable of reacting with the monomerand polymer” is meant that the compound of Formula (I) and the monomerand the polymer will have compatible chemical functionality that canundergo reaction. In other words, each of the monomer and the polymerwill have compatible chemical functionality that can undergo reactionwith relevant functional groups of the compound of Formula (I). Forexample, polymer may be prepared by functional groups of the compound ofFormula (I) reacting with functional groups of the monomer (e.g. via apolymerisation reaction). As a further example, polymer may be modifiedby functional groups of the compound of Formula (I) reacting withfunctional groups of the polymer that is to be modified. Such reactionsmay be promoted by any suitable means, for example by melt mixing thecomponents or by combining the components in a suitable solvent.

In another aspect, the present invention provides for use of a polymer,which comprises as part of its polymer backbone a moiety of Formula(II), to modify one or more other polymers:

where one of R⁶ to R¹⁰ represents A-O— and one of R⁶ to R¹⁰ represents—O—B and the remainder of R⁶ to R¹⁰ represent H, where A and B representthe remainder of the polymer backbone and may be the same or different.

For convenience, polymer which comprises as part of its polymer backbonea moiety of Formula (II) may herein be referred to as the “polymer ofFormula (II)”.

By a polymer of Formula (II) being used to modify one or more otherpolymers is meant that the physical and/or chemical properties of theone or more other polymers are altered by the polymer of Formula (II).

Modification of the one or more other polymers may be non-reactive orreactive in nature. For example, modification may be achieved by meltmixing or blending the one or more other polymers that is to be modifiedwith the polymer of Formula (II). The resulting melt mixed polymercomposition may be an intimate and integral blend of each polymer (i.e.non-reactive in nature), or it may comprise polymer that has formed as aresult of a reaction between the polymers (i.e. reactive in nature).Where the modification is reactive in nature, the polymer of Formula(II) and the one or more other polymers will of course have compatiblechemical functionality that can facilitate the reaction.

In a yet further aspect, the present invention provides a process formodifying polymer, the process comprising combining a polymer whichcomprises as part of its polymer backbone a moiety of Formula (II),

with one or more other polymers, where one of R⁶ to R¹⁰ represents A-O—and one of R⁶ to R¹⁰ represents —O—B and the remainder of R⁶ to R¹⁰represent H, where A and B represent the remainder of the polymerbackbone and may be the same or different.

By “modifying polymer” in this aspect is meant that the physical and/orchemical properties of the one or more other polymers are altered uponcombining it with the polymer of Formula (II).

By “combining” a polymer of Formula (II) with the one or more otherpolymers is meant that all polymers are combined such that the physicaland/or chemical properties of the one or more other polymers to bemodified are altered. Combining the polymers to achieve this willgenerally be performed in a liquid state, for example by melt mixing thepolymers or by dissolving the polymers in a suitable solvent(s).

The act of combining the polymers may be reactive or non-reactive innature as described herein in connection with the modifying polymer.

In a still further aspect, the present invention provides a process forproducing polymer comprising as part of its polymer backbone a moiety ofFormula (II):

where one of R⁶ to R¹⁰ represents A-O— and one of R⁶ to R¹⁰ represents—O—B and the remainder of R⁶ to R¹⁰ represent H, where A and B representthe remainder of the polymer backbone and may be the same or different,the process comprising polymerising one or more compounds of Formula (I)with monomer:

where one of R¹ to R⁵ represents X—O— and one of R¹ to R⁵ represents—O—Y and the remainder of R¹ to R⁵ represent H, where X and Y may be thesame or different and represent H or a group comprising functionalitywhich is capable of reacting with the monomer.

By the compound of Formula (I) having “a group comprising functionalitywhich is capable of reacting with the monomer” is meant that the groupwill have compatible chemical functionality that can react with themonomer so as to form the polymer.

Accordingly, the expression “compatible chemical functionality” isintended to mean that the group and the monomer have functionality of atype that can react with each other so as to form the polymer.

The compounds of Formula (I) may react with themselves or othercompounds of Formula (I) to form polymer. In other words, compounds ofFormula (I) may polymerised in there own right, or with co-monomers notof Formula (I), to form polymer.

For avoidance of any doubt, the “moiety of Formula (II)” is intended tobe a reference to:

with A and B being presented in Formula (II) to (i) more clearly depictthat the “moiety” forms part of the polymer backbone, and (ii) definethe nature of the remainder of the polymer backbone. As mentioned,polymer which comprises as part of its polymer backbone a moiety ofFormula (II) may for convenience herein be referred to as a “polymer ofFormula (II)”.

As used herein, the expression forming “part of the polymer backbone”means that the moiety of Formula (II) (i.e. excluding A and B) is partof the string of atoms that are each connected so as to form the polymerchain (i.e. including A and B) which may be linear or branched. In otherwords, the moiety of Formula (II) is not pendant from the polymerbackbone. Despite the moiety of Formula (II) not being pendant from thepolymer backbone, the polymers of the invention may still comprise apendant group which is formed from the compound of Formula (I), so longas the polymer backbone comprises at least one moiety of Formula (II).

Examples of A and B are discussed in more detail below, but includepolyurethane, polycarbonate and polyester polymer chains,polyether-polyurethane, polyester-amides, polyether-polyesters andpolyether-amides.

Depending on the application, the polymer of the invention may have asingle moiety of Formula (II), but more typically the polymer willcomprise a plurality of moieties of Formula (II) (e.g. 10 or more, 25 ormore, 50 or more, 100 or more). Typically each of the plurality ofmoieties of Formula (II) shall be located in the polymer backbone. Inpolymers comprising a plurality of moieties of Formula (II), each moietyof Formula (II) may be the same or different and each group representedby A and B may be the same or different.

For example, the moiety of Formula (II) may, in conjunction with asuitable comonomer, form a repeat unit of a polyester or polyurethane asillustrated below in general formula (IIa) and (IIb), respectively:

where Z is an alkyl, aryl or alkylaryl group wherein, for each repeatunit of the polyester, Z and the moiety of Formula (II) may eachindependently be the same or different;

where Z is an alkyl, aryl or alkylaryl group wherein, for each repeatunit of the polyurethane, Z and the moiety of Formula (II) may eachindependently be the same or different.

Compounds of Formula (I) can be effectively and efficiently used toprepare new polymer materials. Compounds of Formula (I) canadvantageously be prepared from a renewable source and polymer derivedfrom them have been found to exhibit improved stiffness or rigidityrelative to polymers prepared using conventional monomers, includingdiols such as ethylene glycol.

Further aspects of the invention are described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION

A cyclic compound of Formula (I) may for convenience otherwise bereferred to herein as cineole compound. More particularly, where X and Yare each H, the cineole compound may be referred to as cineole diol. Thestructure of cineole is shown below:

Cineole is a natural product that may be isolated from a number ofnatural renewable sources. For example, cineole makes up approximately90% of Eucalyptus oil which is distilled primarily from the leaves oftrees from the genus Eucalyptus.

It will be understood, however, that despite the structural similarityof compounds of Formula (I) to cineole it may be more facile tosynthesise compounds of Formula (I) from compounds that have a greaterdegree of chemical functionality than cineole. Typically this chemicalfunctionality will enable the introduction of the two exocyclic oxygenatoms that are present in compounds of Formula (I). By “exocyclic oxygenatoms” in compounds of Formula (I) is meant the oxygen atoms in “X—O—”and “—O—Y”, to the exclusion of any oxygen atoms that may be present inX and/or Y. These exocyclic oxygen atoms are highlighted in thefollowing structure, which is provided as an example of the compound ofFormula (I):

For example, compounds of Formula (I) may be derived from a number ofsources including the following compounds:

Each of α-pinene and sobrerol possess one or more functional groups, inparticular a double bond, that may enable the introduction of the twoexocyclic oxygen atoms which are present in compounds of Formula (I).

These compounds may be isolated from a number of natural sourcesincluding pine, bay, tea tree, mugwort, sweet basil, wormwood, rosemary,sage and Eucalyptus. Particularly good sources of the compounds are:α-pinene from pine oil, Eucalyptus oil and Kunzea oil; and sobrerol froma number of natural sources and also semi-synthetically from theoxidation of a terpenoid starting material such as α-pinene. Each ofthese natural sources is believed to be renewable. In fact, many ofthese natural sources are harvested in significant commercialquantities.

Those skilled in the art will appreciate that compounds of Formula (I)and Formula (II) will exist in a number of isomeric forms (such asstereoisomers and structural isomers). In particular, the compounds ofthe invention (including monomers and polymers) may exist in one or morestereoisomeric forms (such as enantiomers, diastereomers) and the twoexocyclic oxygen atoms may be located at any two of R¹ to R⁵ (oxystructural isomers) producing substituents A-O— and —O—B at any two ofR⁶ to R¹⁰ following polymerisation. The present invention includeswithin its scope all of these stereoisomeric forms and oxy structuralisomers (and polymers derived therefrom) either isolated (in for exampleenantiomeric isolation) or in combination (including racemic mixturesand polymers derived from mixtures of oxy structural isomers). Althoughspecific features of an isomer of Formula (II) are not particularlyimportant to the working of the invention, it may be the case thatcertain compounds can be more readily prepared with a particularisomeric structure.

In some embodiments X and Y may be independently selected from H andoptionally substituted hydroxyalkyl, hydroxyalkylcarbonyl, aminoalkyl,aminoalkylcarbonyl, carboxyalkyl, carboxyalkylcarbonyl, epoxyalkyl andunsaturated variants thereof such as aminoalkylene. In these cases eachalkyl group, or unsaturated variant thereof, may comprise from 2 to 20,or from 2 to 10 carbon atoms.

In some embodiments, compounds of Formula (I) have a structure selectedfrom the following:

In one embodiment X and Y are each H and the compound of Formula (I) hasthe following general structure:

One particular compound of Formula (I) is known as epomediol or(6R,7S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diol.

Whilst the present invention envisages that compounds of Formula (I) maybe derived by any suitable means, synthetic methodologies which may beused to prepare a specific cineole compound of Formula (I), where X andY are each H, are outlined below by way of example only.

As described in L. A. Popova, V. I. Biba, V. M. Prishchepenko, S. V.Shavyrin and N. G. Kozlov., translated from Zhurnal Obshch Khimii 1991,62(7), 1639-1645 (the entire contents of which is incorporated herein byreference) the cineole diol shown below is derived from α-pinene (viasobrerol):

Another synthetic route to the cineole diol shown above (and below) isdescribed in A. Bhaumik and T. Tatsumi, Journal of Catalysis 1999, 182,349-356 (the entire contents of which is incorporated herein byreference) and begins with the oxidation of sobrerol using a titaniumcatalyst:

The two groups X—O— and —O—Y provide functionality to covalently couplethe cyclic moiety of compounds of Formula (I) into the polymer backbone.For example, where X and Y are each H the cineole compound is providedwith two reactive hydroxyl groups which are available for reaction witha monomer or polymer having compatible chemical functionality.

In some embodiments, it may be desirable to adjust the reactivity of theX and/or Y groups for a given polymerisation. For example, it will beappreciated that when X and Y are H, the resultant secondary alcoholgroups are quite close to the cyclic moiety which may reduce thereactivity of the alcohol groups due to steric hindrance. Where X and Yarc each hydroxyalkyl groups (such as hydroxyethyl groups) the compoundof Formula (I) is similarly provided with two reactive hydroxyl groupswhich, in this case, are primary alcohol groups and are linked to thecyclic moiety of Formula (I) through alkyl groups and the exocyclicoxygen atoms of Formula (I). In that case the primary alcohol groupswill generally be more reactive toward polymerisation than the secondaryalcohol groups.

In another example, where X and Y are each carboxyalkylcarbonyl groupsthe compound of Formula (I) is provided with two reactive carboxylicacid groups which are linked to the cyclic moiety of Formula (I) throughalkyl groups and ester groups which comprise the exocyclic oxygen atomsof Formula (I). It will be understood that a carboxylic acid group istypically electrophilic in reactivity whereas a hydroxyl group istypically nucleophilic in reactivity, and accordingly the X and Y groupsmay be chosen to provide the compound of Formula (I) with the desiredreactivity.

Combinations of reactive functional groups, such as where X is ahydroxyalkyl group and Y is a carboxyalkylcarbonyl group are alsoenvisaged. In each case, the reactive functionality is capable ofreacting with a monomer having compatible chemical functionality.

In one embodiment, Formula (I) is represented by the compound:

and this compound is polymerised with a monomer having compatiblechemical functionality (e.g. a diacid) to form a polymer comprising aspart of its polymer backbone a moiety:

where A and B represent the remainder of the polymer backbone and may bethe same or different.

In another embodiment Formula (I) is represented by the compound:

In that case, each of X and Y represent hydroxyethyl groups. Thoseskilled in the art will appreciate that the hydroxyethyl groups may befurther derivatised such that one or both of the hydroxyl groups areconverted into, for example, acid, amine or cyano groups. For example,the hydroxyethyl derivative may be synthesised as shown below fromcineole diol, and may be further oxidised to form a di-carboxylic acidcompound:

In a further embodiment, Formula (I) is represented by the compound:

In that case, X represents hydroxymethylcarbonyl and Y representscarboxyethylcarbonyl. It will be appreciated that this compound may besynthesised as shown below from cineole diol:

This acid-alcohol compound may self polymerise or be polymerised with aco-monomer comprising compatible chemical functionality (e.g. anacid-alcohol) to form a polymer comprising as part of its polymerbackbone a moiety:

where A and B represent the remainder of the polymer backbone and may bethe same or different.

In some embodiments, it will be appreciated that a homopolymer may beformed. In that respect, where the substituent X—O— of Formula (I) iscapable of reacting with the substituent —O—Y of Formula (I) ahomopolymer may be formed. In the acid-alcohol example directly aboveX—O— is capable of reacting with —O—Y to form a ester linkage.Accordingly the monomer may be self polymerised to form a homopolymerthat will be a polyester in this instance.

The expression “compatible chemical functionality” used herein thereforerefers to chemical functionality of, for example a monomer or a polymer,that is capable of undergoing reaction (such as polymerisation, chaincoupling etc) with reactive functionality of X—O— and/or —O—Y in acompound of Formula (I). The reactive functionality in the X—O— and/or—O—Y groups of compounds of Formula (I) may react with a variety offunctional groups. For example, where X and Y are both H, or X—O— and—O—Y comprise hydroxy groups, the hydroxy groups may react with suchfunctional groups as: isocyanate functionality to form carbamate orurethane linkages; carboxylic acid functionality to produce esterlinkages; carboxylic acid halide functionality to produce esterlinkages; ester functionality to produce new ester linkages; anhydridefunctionality to produce ester linkages; epoxide functionality toproduce ether linkages; alkyl halide functionality to produce etherlinkages; as well as other carboxylic acid derivatives (including carbondioxide and phosgene) to produce carbonate linkages. Accordingly, theexpression “compatible chemical functionality” includes functionality orgroups such as isocyanate, carboxylic acid, carboxylic acid derivativessuch as carboxylic acid halide, ester, anhydride and other carboxylicacid derivative groups.

In other embodiments, the X—O— and/or —O—Y groups may comprisecarboxylic acid functionality, which is capable of undergoing reactionwith “compatible chemical functionality” such as amines, alcohols andacid halides. Likewise the X—O— and/or —O—Y groups may comprise epoxidefunctionality, which is capable of undergoing reaction with “compatiblechemical functionality” such as amines, alcohols and thiols.

Accordingly, the expression “monomer having compatible chemicalfunctionality” or similar expressions such as “monomer which hascompatible chemical functionality” used herein includes monomercomprising one or more chemical functional groups such as isocyanate,carboxylic acid, carboxylic acid derivatives (including carboxylic acidhalide, ester, anhydride groups), amine, alcohol, thiol and combinationsthereof selected as appropriate depending on the nature of the X and/orY groups in Formula (I). Examples of such monomers are polyisocyanates,poly(acid halides), polyacids, carbon dioxide, phosgene (ortriphosgene), polyols, polyamines and polythiols. In each of these casesthe prefix “poly” is used to indicate the presence of 2 or more (forexample in the case of a polyisocyanate, 2 or more isocyanate groups)reactive functional groups. Typically the monomers will comprise 2reactive functional groups, such as a diisocyanate, diacid halide or adiacid. Co-monomers that react with compounds of Formula (I) to formpolymer may also be of Formula (I).

In some embodiments the or each “monomer” which is used to react with acompound of Formula (I) in the polymerisation reaction to form thepolymer may contain at least one group of compatible chemicalfunctionality (as defined herein) in addition to at least one groupwhich is not, of itself, compatible for undergoing reaction with thecompound of Formula (I). Examples of such monomers are hydroxy-acids,amino acids and thio acids. In the case of a hydroxy-acid, thecarboxylic acid is capable of reacting with a hydroxy group of compoundsof Formula (I) (such as when X and/or Y are H) to produce ahydroxy-terminated compound. Likewise in the case of an amino acid, thecarboxylic acid is capable of reacting with a hydroxy group of compoundsof Formula (I) (such as when X and/or Y are H) to produce anamino-hydroxy-terminated compound. Likewise in the case of a thio acid,the carboxylic acid is capable of reacting with a hydroxy group ofcompounds of Formula (I) (such as when X and/or Y are H) to produce athio-hydroxy-terminated compound. These hydroxy/amino/thio terminatedcompounds may subsequently undergo reaction with another monomer bearinga carboxylic acid, isocyanate group, etc. so that the polymer backbonemay comprise one or more ester, amide, thioester, urea, urethane and/orthiocarbamate functional groups. Other monomers may be used whichcontain functionality which undergoes ring opening to produce afunctional group which is not, of itself, compatible for undergoingreaction with compounds of Formula (I). Examples of such monomers arelactones, lactams, cyclic carbonates and cyclic ethers such as epoxides.For example, where X is H, the hydroxyl group may react with a lactonecompound such as y-butyrolactone to produce a hydroxyl-terminatedcompound.

The “remainder” of the polymer backbone, which is represented by A andB, may be any type of polymer, examples of which are: polyurethanes;polyesters (e.g. PET (polyethylene terephthalate), PLGA(poly(lactic-co-glycolic acid)), PLA (polylactic acid), PGA(polyglycolic acid), PHB (polyhydroxybutyrate), PCL (polycaprolactone);and copolymers thereof); polyamides; polycarbonates; polyimides;polyethers; polyepoxys; polyacrylates; polysiloxanes; polyvinyls (e.g.polyvinylalcohol, polyvinylacetate) and combinations thereof. In someembodiments, A and B are each selected from: polyurethanes; polyesters;polyethers; polycarbonates; and combinations thereof. In one embodimentA and/or B represent a polyurethane or polyester. In all cases, A and/orB may comprise a polymerised residue of one or more compounds of Formula(I). For example, A and/or B may be a poly(ethylene-co-cineole diol)terephthalate.

Polymer comprising a moiety of Formula (II) may be linear or branched.Polymer comprising a moiety of Formula (II) may be a crosslinkedpolymer. Crosslinked polymer may be formed, for example, by theintroduction of unsaturation into the polymer backbone or pendant fromthe polymer backbone, from the use of maleic anhydride or vinyl ester,followed by free radical crosslinking Those skilled in the art willappreciate that this form of crosslinking generally requires the use ofa free radical initiating source. Crosslinked polymer may also be formedby the introduction of pendant epoxy groups which may be crosslinkedusing a polyamine.

In some embodiments, the polymer formed may be a linear polyurethane. Alinear polyurethane may be synthesised using equal molar amounts of adiol component and a diisocyanate component. In one embodiment of theinvention the diol component consists 100% of the cyclic compound ofFormula (I) bearing two hydroxyl groups, such as when X and Y are bothH. In this instance, polymerisation of the cyclic compound of Formula(I) with a diisocyanate produces a polyurethane comprising 50 mol %cyclic compound residue and 50 mol % diisocyanate residue. In a furtherembodiment, the diol component may comprise a plurality of diolcompounds where each compound may comprise from 1 to 99 mol % of thediol component. In such an embodiment it will be understood that thecombined total of the diol compounds will add to 100 mol %. For examplethe diol component may comprise 50 mol % of a cyclic compound of Formula(I) bearing two hydroxyl groups and 50 mol % of another diol (e.g.ethylene glycol). Likewise, the diisocyanate component may consist of asingle compound or may comprise two or more diisocyanate compounds whereeach compound may range from 1 to 99 mol % of the diisocyanatecomponent. Similarly, it will be understood that in such an embodimentthe combined total of the diisocyanate compounds will add to 100 mol %.

In some embodiments the polymer formed is a linear polyester. A linearpolyester may be synthesised from equal molar amounts of a diolcomponent and a diacid component (or diester or diacid halide asappropriate). In some embodiments the diol component consists 100% ofthe cyclic compound of Formula (I) bearing two hydroxyl groups, such aswhen

X and Y are both H. In this instance, polymerisation of the cycliccompound of Formula (I) with a diester produces a polyester comprising50 mol % cyclic diol residue and 50 mol % diacid residue. In otherembodiments the diol component may consist of a plurality of diolcompounds where each compound may comprise from 1 to 99 mol % of thediol component. In these embodiments it will be understood that thecombined total of each of the plurality of diol compounds is 100 mol %of the diol component. For example the diol component may consist 50 mol% of a cyclic compound of Formula (I) bearing two hydroxyl groups and 50mol % of another diol. Likewise, the diacid component may consist of asingle compound or may consist of one or more diacid compounds whereeach compound may range from 1 to 99 mol % of the diacid component. Inthese embodiments it will be understood that the combined total of eachof the plurality of diacid compounds is 100 mol % of the diacidcomponent.

Examples of polyisocyanates that may be used to prepare polymers of theinvention include aliphatic, aromatic and cycloaliphatic polyisocyanatesand combinations thereof. Specific polyisocyanates include, but are notlimited to, diisocyanates such as m-phenylene diisocyanate, p-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,1,6-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate,1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate,hexahydro-toluene diisocyanate and its isomers, isophorone diisocyanate,dicyclo-hexylmethane diisocyanates, 1,5-napthylene diisocyanate,4,4′-diphenylmethane diisocyanate, 2,4′ diphenylmethane diisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylenediisocyanate, and 3,3′-dimethyl-diphenylpropane-4,4′-diisocyanate;triisocyanates such as 2,4,6-toluene triisocyanate; polyisocyanates suchas 4,4′-dimethyl-diphenylmethane-2,2′,5,5′-tetraisocyanate,polymethylene polyphenyl-polyisocyanates and alkyl esters of lysinediisocyanate (for example ethyl ester of lysine diisocyanate—ELDI); andcombinations thereof.

Examples of polyacids that may be used to prepare polymers of theinvention include aliphatic, aromatic and cycloaliphatic polyacids andcombinations thereof. Specific polyacids include, but are not limited tothe following, oxalic acid, fumaric acid, maleic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, phthalic acid, dodecanediacid, isophthalic acid,terephthalic acid, dodecylsuccinic acid, napthalene-2,6-dicarboxylicacid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid,fumaric acid, itaconic acid, malonic acid, mesaconic acid. Esters,carboxylic acid halides and anhydrides of the above diacids are alsosuitable in the process of the invention.

Examples of polyols that may be used in combination with the cineolecompounds of Formula (I) (in those instances where they bear twohydroxyl groups) to prepare polymers of the invention include aliphaticglycols such as: ethylene glycol, propylene glycol, butane-1,4-diol;glycol ethers such as diethylene glycol, dipropylene glycol and thelike; and higher functionality polyols materials such as glycerol,sorbitol, pentaerythritol; and polyester polyols such aspolycaprloactone diols. Also suitable are dihydroxy compounds such asbisphenol-A and hydrogenated bisphenol-A. Generally, the polyol willhave from 2 to 20 or 2 to 10 carbon atoms and 2 to 4 hydroxy groups.

Where a polyfunctional compound having more than two reactive functionalgroups (e.g. triol, tetraol, triacid, tetraacid, triisocyanate,tetraisocyanate, etc) is used in accordance with the invention, thoseskilled in the art will appreciate that the molar fractions required foreach monomer in a given reaction will need to be adjusted accordingly.Such higher polyfunctional compounds (i.e. >2 functional groups) willalso typically introduce a branch point within the resulting polymerbackbone.

As foreshadowed above, polymerisation of cyclic compounds of Formula(I), which bear two hydroxyl groups, with a polyisocyanate or polyacid(or derivatives thereof such as an ester or acid halide) may also takeplace in the presence of one or more other types of other polyols.Certain polyols can be referred to in the art as chain extenders.

Examples of polyols known in the art as chain extending polyols includeα,ω-alkanediols such as ethylene glycol, 1,3-propanediol and1,6-hexanediol.

Techniques, equipment and reagents well known in the art canadvantageously be used to prepare or modify polymers in accordance withthe invention. The polymerisation/modification may be carried out in arange of different equipment including batch kettles, static mixers,injection moulders or extruders.

In some embodiments, it may be advantageous to heat the reagents priorto or during the reaction process to improve their solubility or toenhance their reactivity. A catalyst, such as a polycondensationcatalyst, well known to those skilled in the art may be included in thereaction mixture to increase the rate of polymerisation. Typicalcondensation catalysts include Lewis acids such as antimony trioxide,titanium oxide and dibutyl tindilaurate.

The polymerisation may also be conducted in solvent to help increase therate of polymerisation. The solvent will generally be selected to haveonly minimal solubility with any condensate (such as water or lowmolecular weight alcohol) which may be formed in the case of polyesterformation. For example the reaction may be carried out in toluene and atoluene/condensate mixture distilled off continuously and the condensateallowed to separate in a Dean—Stark trap.

In some embodiments, polyurethanes may be prepared batch wise by mixingall components together and waiting until an exotherm occurs followed bycasting the mixture into a container. The mixture can be subsequentlyheated to drive the reaction. When adopting this approach, thecomponents to be mixed may first be made up into two parts beforemixing: Part-1 may include a cyclic compound of Formula (I) bearing twohydroxyl groups and optionally one or more of a polyol, a chainextender, blowing agent (e.g. water), catalyst, and surfactants etc.Part-2 will generally comprise the polyisocyanate. Part-1 or Part-2 mayalso contain other additives such as fillers, pigments etc.

The polyurethanes may also be prepared as a prepolymer that issubsequently reacted with a chain extender. For example, throughsuitable adjustment of molar ratios, an isocyanate terminatedpre-polymer may be prepared by mixing Parts-1 and -2 mentioned above.The isocyanate terminated polymer may then be reacted with a chainextender/branching molecule such as a short chain diol (e.g.1,4-butanediol) or a higher polyol (such as a triol). Alternatively,through suitable adjustment of molar ratios, the prepolymer may beproduced such that it is hydroxy terminated. This hydroxy terminatedprepolymer may then be reacted with a polyisocyanate to produce thedesired polyurethane.

Where polyesters are prepared using a carboxylic acid halide monomer,those skilled in the art will appreciate that the reaction is driven, atleast in part, by the formation and removal of HX (where X is a halide).For example, if a diacid chloride comonomer is reacted with a compoundof Formula (I) bearing two hydroxyl groups, HCl will be liberated fromthe reaction. Such a reaction may be carried out in solution at anelevated temperature to drive the reaction. It is also possible to addan appropriate base to form a salt with the liberated acid halide. Forexample an excess of triethylamine may be included in a reaction mixturecontaining a 1:1 molar ratio of a di-acid chloride co-monomer and acompound of Formula (I) bearing two hydroxyl groups. The reaction willafford the desired polymer and a triethylamine hydrochloride salt.Despite the fact that the reaction of an alcohol and an acid halide doesnot liberate a condensate such as water or alcohol, the formation of theester product may nonetheless be regarded as a condensation reaction tothe extent that a condensate is typically formed in the prior conversionof a carboxylic acid into the acid halide.

In a similar way to the expressions “monomer having compatible chemicalfunctionality” and variants thereof such as “monomer which hascompatible chemical functionality” are defined herein, the expressions“polymer having compatible chemical functionality” and variants thereofsuch as “polymer which has compatible chemical functionality” usedherein refer to polymers having a functionality that can react withreactive functionality in a compound of Formula (I) or a polymer ofFormula (II).

Examples of polymers that may be modified with a compound of Formula (I)or a polymer of Formula (II) in accordance with the invention includepolyesters, polyurethanes and polycarbonates.

In that respect, the groups X—O— and/or —O—Y in cineole compounds ofFormula (I) may be used to promote reaction with compatible chemicalfunctionality present in one or more polymers. In particular, thecineole compounds may advantageously be used to modify the molecularstructure and hence properties of preformed polymers.

The invention provides polymer blends comprising the polymer of theinvention and at least one other polymer. Standard blending techniquesmay be used including melt mixing, such as extrusion. The polymer blendmay also be a physical blend (i.e. non-melt mixed).

A compound of Formula (I) is used to react with and covalently couple tothe polymer to be modified.

The polymer of Formula (II) may modify one or more other polymers byreaction or by simply being melt blended therewith.

Where a compound of Formula (I) or a polymer of Formula (II) reacts withand modifies the molecular structure of the one or more other polymers,a residue of the compound or a portion of the polymer of Formula (II)typically forms part of the modified polymer's backbone. For example,where the X—O— and —O—Y groups in the cineole compounds comprisehydroxyl groups the cineole compounds may react with, and becomeincorporated in, a polyester through alcoholysis. Such reactions may bepromoted using reactive extrusion techniques known in the art. In thatcase, the cineole compounds may be melt mixed with a polyester topromote insertion of the diol within the backbone of the polyester.Other functionality within the X—O— and/or —O—Y groups may additionallyor alternatively enable the insertion of the cineole compound of Formula(I) into the backbone of the one or more polymers.

Where the cineole compound of Formula (I) is used to modify a preformedpolymer, the modification process can be carried out using equipment andtechniques known by those skilled in the art. For example, the cineolecompound may be melt mixed with one or more polymers using continuousextrusion equipment such as twin screw extruders, single screwextruders, other multiple screw extruders and Farell mixers.Semi-continuous or batch processing equipment may also be used toachieve melt mixing. Examples of such equipment include injectionmoulders, Banbury mixers and batch mixers. Static melt mixing equipmentmay also be used.

Reaction of the cineole compound of Formula (I) with a polymer, such asa polyester, may result in a reduction in the polymer's molecularweight. If desired, the molecular weight of the polymer can besubsequently increased using techniques known in the art. For example,where the polymer that is reacted with the cineole compound is apolyester, and the cineole compound bears two hydroxyl groups, theresulting reaction mixture may be subjected to a solid statepolymerisation process.

Chain coupling agents may also be introduced in the reaction to offsetany reduction in molecular weight. Such agents include polyfunctionalacid anhydrides, epoxy compounds, oxazoline derivatives, oxazolinonederivatives, lactams, isocyanates, lactones and related species. In someembodiments, the compound of Formula (I) may itself comprise suchfunctionality in the X—O— and —O—Y groups.

Examples of coupling agents also include one or more of the following:

Polyepoxides such as bis(3,4-epoxycyclohexylmethyl) adipate;N,N-diglycidyl benzamide (and related diepoxies); N,N-diglycidyl anilineand derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid orisocyanuric acid derivatives; N,N-diglycidyl diimides; N,N-diglycidylimidazolones; epoxy novolaks; phenyl glycidyl ether; diethyleneglycoldiglycidyl ether; Epikote 815 (diglycidyl ether of bisphenolA-epichlorohydrin oligomer).

Polyoxazolines/Polyoxazolones such as 2,2-bis(-oxazoline); 1,3-phenylenebis(2-oxazoline-2), 1,2-bis(2-oxazolinyl-2)ethane;2-phenyl-1,3-oxazoline; 2,2′-bis(5,6-dihydro-4H-1,3-oxazoline);N,N′-hexamethylenebis (carbamoyl-2-oxazoline; bis[5(4H)-oxazolone);bis(4H-3,1benzoxazin-4-one); 2,2′-bis(H-3,1-benzozin-4-one).

Polyfunctional acid anhydrides such as pyromellitic dianhydride,benzophenonetetracarboxylic acid dianhydride,cyclopentanetetracarboxylic dianhydride, diphenyl sulphonetetracarboxylic dianhydride,5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylicdianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol-A bisetherdianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,2,3,6,7-naphthalenetetracarboxylic acid dianhydride,bis(3,4-dicarboxyphenyl)sulphone dianhydride,1,2,5,6-naphthalenetetracarboxylic acid dianhydride,2,2′,3,3′-biphenyltetracarboxylic acid, hydroquinone bisetherdianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride,1,2,3,4-cyclobutanetetracarboxylic acid dianhydride,3,4-dicarboxy-1,2,3,4-tetrahydro-lnaphthalene-succinic acid dianhydride,bicyclo(2,2)oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride,2,2-bis(3,4dicarboxyphenyl)propane dianhydride, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, 4,4′-oxydiphthalicdianhydride (ODPA), and ethylenediamine tetraacetic acid dianhydride(EDTAh). It is also possible to use acid anhydride containing polymersor copolymers as the acid anhydride component.

Preferred polyfunctional acid anhydrides include pyromelliticdianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,1,2,3,4-cyclobutanetetracarboxylic acid dianhydride andtetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride. Mostpreferably the polyfunctional acid anhydride is pyromelliticdianhydride.

Polyacyllactams such as N,N′-terephthaloylbis(caprolactarn) andN,N′-terephthaloylbis(laurolactam).

The polymer of Formula (II) may be used to modify the molecularstructure and hence properties of preformed polymers. For example, meltmixing a polymer of Formula (II) in the form of a polyester with aanother polyester will generally lead to the incorporation of the cyclicmoiety of Formula (II) into the preformed polyester. Such insertion mayalso result in a loss in molecular weight of the other polyester whichmay be offset as herein described.

In some embodiments, it may be desirable to promote a degree of controlover the way in which the cyclic moiety of the polymer of Formula (II)is incorporated into the one or more other polymers, particularly withrespect to the block character of the polymer of Formula (II) comprisingthe moiety or moieties to be incorporated. In these embodiments, it maybe possible to retain any block character using a polymer of Formula(II) that can resist fragmentation under the conditions employed. Forexample, the polymer of Formula (II) may be a polyester having estergroups in the polymer backbone that are sterically hindered andresistant to transesterification.

Compounds of Formula (I) can provide polymers of the invention with oneor more advantageous properties. Without wishing to be limited by theoryit is believed that the bicyclic structure of the compound of Formula(I) provides the polymers with advantageous mechanical properties, suchas stiffness or rigidity. It is also believed that these advantageousproperties are enhanced when the molar fraction of the moiety of Formula(II) in the polymer backbone is increased.

The polymers of the invention may be formed into a range of products.Examples of such products are sheets, fibres and films which may beformed through injection moulding, extrusion moulding, rotationmoulding, foam moulding, calendar moulding, blow moulding,thermoforming, compaction and melt spinning, for example.

This polymer of the invention may be blended with one or more additivestypically suited to polymer production. Examples of such additivesinclude extenders, UV stabilizers, antioxidants, lubricants, flowmodifiers, pigments, dyes, colourants, fillers, plasticizers, opticalbrighteners, fire retardants, impact modifiers, reinforcing agents (suchas glass fibres, kaolin, mica), anti-static agents, and blowing agents.

In this specification “optionally substituted” is taken to mean that agroup may or may not be substituted or fused (so as to form a condensedpolycyclic group) with one, two, three or more of organic and inorganicgroups (i.e. the optional substituent) including those selected from:alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl,acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl,halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl,haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy,hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarbocyclyl,hydroxyaryl, hydroxyheterocyclyl, hydroxyheteroaryl, hydroxyacyl,hydroxyaralkyl, alkoxyalkyl, alkoxyalkenyl, alkoxyalkynyl,alkoxycarbocyclyl, alkoxyaryl, alkoxyheterocyclyl, alkoxyheteroaryl,alkoxyacyl, alkoxyaralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy,carbocyclyloxy, aralkyloxy, heteroaryloxy, heterocyclyloxy, acyloxy,haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy,halocarbocyclyloxy, haloaralkyloxy, haloheteroaryloxy,haloheterocyclyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl,nitroalkynyl, nitroaryl, nitroheterocyclyl, nitroheteroayl,nitrocarbocyclyl, nitroacyl, nitroaralkyl, amino (NH₂), alkylamino,dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino,aralkylamino, diaralkylamino, acylamino, diacylamino, heterocyclamino,heteroarylamino, carboxy, carboxyester, amido, alkylsulphonyloxy,arylsulphenyloxy, alkylsulphenyl, arylsulphenyl, thio, alkylthio,alkenylthio, alkynylthio, arylthio, aralkylthio, carbocyclylthio,heterocyclylthio, heteroarylthio, acylthio, sulfoxide, sulfonyl,sulfonamide, aminoalkyl, aminoalkenyl, aminoalkynyl, aminocarbocyclyl,aminoaryl, aminoheterocyclyl, aminoheteroaryl, aminoacyl, aminoaralkyl,thioalkyl, thioalkenyl, thioalkynyl, thiocarbocyclyl, thioaryl,thioheterocyclyl, thioheteroaryl, thioacyl, thioaralkyl, carboxyalkyl,carboxyalkenyl, carboxyalkynyl, carboxycarbocyclyl, carboxyaryl,carboxyheterocyclyl, carboxyheteroaryl, carboxyacyl, carboxyaralkyl,carboxyesteralkyl, carboxyesteralkenyl, carboxyesteralkynyl,carboxyestercarbocyclyl, carboxyesteraryl, carboxyesterheterocyclyl,carboxyesterheteroaryl, carboxyesteracyl, carboxyesteraralkyl,amidoalkyl, amidoalkenyl, amidoalkynyl, amidocarbocyclyl, amidoaryl,amidoheterocyclyl, amidoheteroaryl, amidoacyl, amidoaralkyl,formylalkyl, formylalkenyl, formylalkynyl, formylcarbocyclyl,formylaryl, formylheterocyclyl, formylheteroaryl, formylacyl,formylaralkyl, acylalkyl, acylalkenyl, acylalkynyl, acylcarbocyclyl,acylacyl, acylheterocyclyl, acylheteroaryl, acylacyl, acylaralkyl,sulfoxidealkyl, sulfoxidealkenyl, sulfoxidealkynyl,sulfoxidecarbocyclyl, sulfoxidearyl, sulfoxideheterocyclyl,sulfoxideheteroaryl, sulfoxideacyl, sulfoxidearalkyl, sulfonylalkyl,sulfonylalkenyl, sulfonylalkynyl, sulfonylcarbocyclyl, sulfonylaryl,sulfonylheterocyclyl, sulfonylheteroaryl, sulfonylacyl, sulfonylaralkyl,sulfonamidoalkyl, sulfonamidoalkenyl, sulfonamidoalkynyl,sulfonamidocarbocyclyl, sulfonamidoaryl, sulfonamidoheterocyclyl,sulfonamidoheteroaryl, sulfonamidoacyl, sulfonamidoaralkyl, nitroalkyl,nitroalkenyl, nitroalkynyl, nitrocarbocyclyl, nitroaryl,nitroheterocyclyl, nitroheteroaryl, nitroacyl, nitroaralkyl, cyano,sulfate and phosphate groups.

In some embodiments, it may be desirable that a group is optionallysubstituted with a polymer chain. An example of such a polymer chainincludes a polyester, polyurethane, or copolymers thereof.

Preferred optional substituents include alkyl, (e.g. C₁₋₆ alkyl such asmethyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl), hydroxyalkyl (e.g.

hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g.methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl,ethoxypropyl etc) alkoxy (e.g. C₁₋₆ alkoxy such as methoxy, ethoxy,propoxy, butoxy, cyclopropoxy, cyclobutoxy), halo, trifluoromethyl,trich1oromethyl, tribromomethyl, hydroxy, phenyl (which itself may befurther substituted e.g., by C₁₋₆ alkyl, halo, hydroxy, hydroxyC₁₋₆alkyl, C₁₋₆ alkoxy, haloC₁₋₆alkyl, cyano, nitro OC(O)C₁₋₆ alkyl, andamino), benzyl (wherein benzyl itself may be further substituted e.g.,by C₁₋₆ alkyl, halo, hydroxy, hydroxyC₁₋₆alkyl, C₁₋₆ alkoxy, haloC₁₋₆alkyl, cyano, nitro OC(O)C₁₋₆ alkyl, and amino), phenoxy (wherein phenylitself may be further substituted e.g., by C₁₋₆ alkyl, halo, hydroxy,hydroxyC₁₋₆ alkyl, C₁₋₆ alkoxy, haloC₁₋₆ alkyl, cyano, nitro OC(O)C₁₋₆alkyl, and amino), benzyloxy (wherein benzyl itself may be furthersubstituted e.g., by C₁₋₆ alkyl, halo, hydroxy, hydroxyC₁₋₆ alkyl, C₁₋₆alkoxy, haloC₁₋₆ alkyl, cyano, nitro OC(O)C₁₋₆ alkyl, and amino), amino,alkylamino (e.g. C₁₋₆ alkyl, such as methylamino, ethylamino,propylamino etc), dialkylamino (e.g. C₁₋₆ alkyl, such as dimethylamino,diethylamino, dipropylamino), acylamino (e.g. NHC(O)CH₃), phenylamino(wherein phenyl itself may be further substituted e.g., by C₁₋₆ alkyl,halo, hydroxy hydroxyC₁₋₆ alkyl, C₁₋₆ alkoxy, haloC₁₋₆ alkyl, cyano,nitro OC(O)C₁₋₆ alkyl, and amino), nitro, formyl, -C(O)-alkyl (e.g. C₁₋₆alkyl, such as acetyl), O—C(O)-alkyl (e.g. C₁₋₆alkyl, such asacetyloxy), benzoyl (wherein the phenyl group itself may be furthersubstituted e.g., by C₁₋₆ alkyl, halo, hydroxy hydroxyC₁₋₆ alkyl, C₁₋₆alkoxy, haloC₁₋₆ alkyl, cyano, nitro OC(O)C₁₋₆alkyl, and amino),replacement of CH₂ with C═O, CO₂H, CO₂alkyl (e.g. C₁₋₆ alkyl such asmethyl ester, ethyl ester, propyl ester, butyl ester), CO₂phenyl(wherein phenyl itself may be further substituted e.g., by C₁₋₆ alkyl,halo, hydroxy, hydroxyl C₁₋₆ alkyl, C₁₋₆ alkoxy, halo C₁₋₆ alkyl, cyano,nitro OC(O)C₁₋₆ alkyl, and amino), CONH₂, CONHphenyl (wherein phenylitself may be further substituted e.g., by C₁₋₆ alkyl, halo, hydroxy,hydroxyl C₁₋₆ alkyl, C₁₋₆ alkoxy, halo C₁₋₆ alkyl, cyano, nitroOC(O)C₁₋₆ alkyl, and amino), CONHbenzyl (wherein benzyl itself may befurther substituted e.g., by C₁₋₆ alkyl, halo, hydroxy hydroxyl C₁₋₆alkyl, C₁₋₆ alkoxy, halo C₁₋₆ alkyl, cyano, nitro OC(O)C₁₋₆ alkyl, andamino), CONHalkyl (e.g. C₁₋₆ alkyl such as methyl ester, ethyl ester,propyl ester, butyl amide) CONHdialkyl (e.g. C₁₋₆ alkyl) aminoalkyl(e.g., FIN C₁₋₆ alkyl-, C₁₋₆alkylHN—C₁₋₆ alkyl- and (C₁₋₆ alkyl)₂N—C₁₋₆alkyl-), thioalkyl (e.g., HS C₁₋₆ alkyl-), carboxyalkyl (e.g., HO₂CC₁₋₆alkyl-), carboxyesteralkyl (e.g., C₁₋₆ alkylO₂CC₁₋₆ alkyl-), aminoalkyl(e.g., H₂N(O)CC₁₋₆ alkyl-, H(C₁₋₆ alkyl)N(O)CC₁₋₆ alkyl-), formylalkyl(e.g., OHCC₁₋₆alkyl-), acylalkyl (e.g., C₁₋₆ alkyl(O)CC₁₋₆ alkyl-),nitroalkyl (e.g., O₂NC₁₋₆ alkyl-), sulfoxidealkyl (e.g., R³(O)SC₁₋₆alkyl, such as C₁₋₆ alkyl(O)SC₁₋₆ alkyl-), sulfonylalkyl (e.g.,R³(O)₂SC₁₋₆ alkyl-such as C₁₋₆ alkyl(O)₂SC₁₋₆ alkyl-), sulfonamidoalkyl(e.g., 2HRN(O)SC₁₋₆ alkyl, H(C₁₋₆ alkyl)N(O)SC₁₋₆ alkyl-).

As used herein, the term “alkyl”, used either alone or in compound wordsdenotes straight chain, branched or cyclic alkyl, for example C₁₋₄₀alkyl, or C₁₋₂₀ or C₁₋₁₀. Examples of straight chain and branched alkylinclude methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl,n-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl,4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl,1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl,2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl,1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethyl-pentyl,1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl,6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-,3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2-or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl,1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl,undecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-,4-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-,9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-,2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl,1-2-pentylheptyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonoadecyl, eicosyl and the like. Examples ofcyclic alkyl include mono- or polycyclic alkyl groups such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group isreferred to generally as “propyl”, butyl” etc, it will be understoodthat this can refer to any of straight, branched and cyclic isomerswhere appropriate. An alkyl group may be optionally substituted by oneor more optional substituents as herein defined.

As used herein, term “alkenyl” denotes groups formed from straightchain, branched or cyclic hydrocarbon residues containing at least onecarbon to carbon double bond including ethylenically mono-, di- orpolyunsaturated alkyl or cycloalkyl groups as previously defined, forexample C₂₋₄₀ alkenyl, or C₂₋₂₀ or C₂₋₁₀. Thus, alkenyl is intended toinclude propenyl, butylenyl, pentenyl, hexaenyl, heptaenyl, octaenyl,nonaenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nondecenyl,eicosenyl hydrocarbon groups with one or more carbon to carbon doublebonds. Examples of alkenyl include vinyl, allyl, 1-methylvinyl, butenyl,iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl,1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl,3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl,1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl,1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl,1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl,1,3,5-cycloheptatrienyl and 1,3,5,7-cyclooctatetraenyl. An alkenyl groupmay be optionally substituted by one or more optional substituents asherein defined.

As used herein the term “alkynyl” denotes groups formed from straightchain, branched or cyclic hydrocarbon residues containing at least onecarbon-carbon triple bond including ethylenically mono-, di- orpolyunsaturated alkyl or cycloalkyl groups as previously defined, forexample, C₂₋₄₀ alkenyl, or C₂₋₂₀ or C₂₋₁₀. Thus, alkynyl is intended toinclude propynyl, butylynyl, pentynyl, hexaynyl, heptaynyl, octaynyl,nonaynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nondecynyl,eicosynyl hydrocarbon groups with one or more carbon to carbon triplebonds. Examples of alkynyl include ethynyl, 1-propynyl, 2-propynyl, andbutynyl isomers, and pentynyl isomers. An alkynyl group may beoptionally substituted by one or more optional substituents as hereindefined.

An alkenyl group may comprise a carbon to carbon triple bond and analkynyl group may comprise a carbon to carbon double bond (i.e. socalled ene-yne or yne-ene groups).

As used herein, the term “aryl” (or “carboaryl)” denotes any of single,polynuclear, conjugated and fused residues of aromatic hydrocarbon ringsystems. Examples of aryl include phenyl, biphenyl, terphenyl,quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl,dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl,fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl. Preferred aryl includephenyl and naphthyl. An aryl group may be optionally substituted by oneor more optional substituents as herein defined.

As used herein, the terms “alkylene”, “alkenylene”, and “arylene” areintended to denote the divalent forms of “alkyl”, “alkenyl”, and “aryl”,respectively, as herein defined.

The term “halogen” (“halo”) denotes fluorine, chlorine, bromine oriodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine,bromine or iodine.

The term “carbocyclyl” includes any of non-aromatic monocyclic,polycyclic, fused or conjugated hydrocarbon residues, preferably C₃₋₂₀(e.g. C₃₋₁₀ or C₃₋₈). The rings may be saturated, e.g. cycloalkyl, ormay possess one or more double bonds (cycloalkenyl) and/or one or moretriple bonds (cycloalkynyl). Particularly preferred carbocyclyl moietiesare 5-6-membered or 9-10 membered ring systems. Suitable examplesinclude cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl,cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl,indanyl, decalinyl and indenyl.

The term “heterocyclyl” when used alone or in compound words includesany of monocyclic, polycyclic, fused or conjugated hydrocarbon residues,preferably C₃₋₂₀ (e.g. C₃₋₁₀ or C₃₋₈) wherein one or more carbon atomsare replaced by a heteroatom so as to provide a non-aromatic residue.Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S.Where two or more carbon atoms are replaced, this may be by two or moreof the same heteroatom or by different heteroatoms. The heterocyclylgroup may be saturated or partially unsaturated, i.e. possess one ormore double bonds. Particularly preferred heterocyclyl are 5-6 and 9-10membered heterocyclyl. Suitable examples of heterocyclyl groups mayinclude azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl,2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl,morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl,thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl,tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl,thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl,thiomorpholinyl, oxathianyl, dithianyl, trioxanyl, thiadiazinyl,dithiazinyl, trithianyl, azepinyl, oxepinyl, thiepinyl, indenyl,indanyl, 3H-indolyl, isoindolinyl, 4H-quinolazinyl, chromenyl,chromanyl, isochromanyl, pyranyl and dihydropyranyl.

The term “heteroaryl” includes any of monocyclic, polycyclic, fused orconjugated hydrocarbon residues, wherein one or more carbon atoms arereplaced by a heteroatom so as to provide an aromatic residue. Preferredheteroaryl have 3-20 ring atoms, e.g. 3-10. Particularly preferredheteroaryl are 5-6 and 9-10 membered bicyclic ring systems.

Suitable heteroatoms include, O, N, S, P and Se, particularly O, N andS. Where two or more carbon atoms are replaced, this may be by two ormore of the same heteroatom or by different heteroatoms. Suitableexamples of heteroaryl groups may include pyridyl, pyrrolyl, thienyl,imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl,isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl,pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl,1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl,thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl,oxatriazolyl, triazinyl, and furazanyl.

The term “acyl” either alone or in compound words denotes a groupcontaining the agent C═O (and not being a carboxylic acid, ester oramide) Preferred acyl includes C(O)—R^(x), wherein R^(x) is hydrogen oran alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, orheterocyclyl residue. Examples of acyl include formyl, straight chain orbranched alkanoyl (e.g. C₁₋₂₀) such as, acetyl, propanoyl, butanoyl,2-methylpropanoyl, pentanoyl, 2,2-dimethylpropanoyl, hexanoyl,heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl,tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl,octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such ascyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl andcyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl;aralkanoyl such as phenylalkanoyl (e.g. phenylacetyl, phenylpropanoyl,phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl)and naphthylalkanoyl (e.g. naphthylacetyl, naphthylpropanoyl andnaphthylbutanoyl]; aralkenoyl such as phenylalkenoyl (e.g.phenylpropenoyl, phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl andphenyihexenoyl and naphthylalkenoyl (e.g. naphthylpropenoyl,naphthylbutenoyl and naphthylpentenoyl); aryloxyalkanoyl such asphenoxyacetyl and phenoxypropionyl; arylthiocarbamoyl such asphenylthiocarbamoyl; arylglyoxyloyl such as phenylglyoxyloyl andnaphthylglyoxyloyl; arylsulfonyl such as phenylsulfonyl andnapthylsulfonyl; heterocycliccarbonyl; heterocyclicalkanoyl such asthienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl,thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl andtetrazolylacetyl; heterocyclicalkenoyl such as heterocyclicpropenoyl,heterocyclicbutenoyl, heterocyclicpentenoyl and heterocyclichexenoyl;and heterocyclicglyoxyloyl such as thiazolyglyoxyloyl andthienylglyoxyloyl. The R^(x) residue may be optionally substituted asdescribed herein.

The term “sulfoxide”, either alone or in a compound word, refers to agroup —S(O)R^(y) wherein R^(y) is selected from hydrogen, alkyl,alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, andaralkyl. Examples of preferred R^(y) include C₁₋₂₀alkyl, phenyl andbenzyl.

The term “sulfonyl”, either alone or in a compound word, refers to agroup —S(O)₂—R^(y), wherein R^(y) is selected from hydrogen, alkyl,alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl andaralkyl. Examples of preferred R^(y) include C₁₋₂₀alkyl, phenyl andbenzyl.

The term “sulfonamide”, either alone or in a compound word, refers to agroup —S(O)NR^(y)R^(y) wherein each R^(y) is independently selected fromhydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,carbocyclyl, and aralkyl. Examples of preferred R^(y) includeC₁₋₂₀alkyl, phenyl and benzyl. In a preferred embodiment at least oneR^(y) is hydrogen. In another form, both R^(y) are hydrogen.

The term, “amino” is used here in its broadest sense as understood inthe art and includes groups of the formula NR^(A)R^(B) wherein R^(A) andR^(B) may be any independently selected from hydrogen, alkyl, alkenyl,alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.R^(A) and R^(B), together with the nitrogen to which they are attached,may also form a monocyclic, or polycyclic ring system e.g. a 3-10membered ring, particularly, 5-6 and 9-10 membered systems. Examples of“amino” include NH₂, NHalkyl (e.g. C₁₋₂₀alkyl), NHaryl (e.g. NHphenyl),NHaralkyl (e.g. NHbenzyl), NHacyl (e.g. NHC(O)C₁₋₂₀alkyl, NHC(O)phenyl),Nalkylalkyl (wherein each alkyl, for example C₁₋₂₀, may be the same ordifferent) and 5 or 6 membered rings, optionally containing one or moresame or different heteroatoms (e.g. O, N and S).

The term “amido” is used here in its broadest sense as understood in theart and includes groups having the formula C(O)NR^(A)R^(B), whereinR^(A) and R^(B) are as defined as above. Examples of amido includeC(O)NH₂, C(O)NHalkyl (e.g. C₁₋₂₀alkyl), C(O)NHaryl (e.g. C(O)NHphenyl),C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.C(O)NHC(O)C₁₋₂₀alkyl, C(O)NHC(O)phenyl), C(O)Nalkylalkyl (wherein eachalkyl, for example C₁₋₂₀, may be the same or different) and 5 or 6membered rings, optionally containing one or more same or differentheteroatoms (e.g. O, N and S).

The term “carboxy ester” is used here in its broadest sense asunderstood in the art and includes groups having the formula CO₂R^(z),wherein R^(z) may be selected from groups including alkyl, alkenyl,alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.Examples of carboxy ester include CO₂C₁₋₂₀alkyl, CO₂aryl (e.g.,CO₂phenyl), CO₂aralkyl (e.g. CO₂ benzyl).

The term “heteroatom” or “hetero” as used herein in its broadest senserefers to any atom other than a carbon atom which may be a member of acyclic organic group. Particular examples of heteroatoms includenitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium andtellurium, more particularly nitrogen, oxygen and sulfur.

The present invention will hereinafter be further described withreference to the following non-limiting examples.

EXAMPLES

General

Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200spectrometer, operating at 400 MHz and 200 MHz. All spectra wereobtained at 23° C. unless specified. Chemical shifts are reported inparts per million (ppm) on the 6 scale and relative to the chloroformpeak at 7.26 ppm (¹H) or the TMS peak at 0.00 ppm (¹H). Oven driedglassware was used in all reactions carried out under an inertatmosphere (either dry nitrogen or argon). All starting materials andreagents were obtained commercially unless otherwise stated. Removal ofsolvents “under reduced pressure” refers to the process of bulk solventremoval by rotary evaporation (low vacuum pump) followed by applicationof high vacuum pump (oil pump) for a minimum of 30 min. Analytical thinlayer chromatography (TLC) was performed on plastic-backed MerckKieselgel KG60F₂₅₄ silica plates and visualised using short waveultraviolet light, potassium permanganate or phosphomolybdate dip. Flashchromatography was performed using 230-400 mesh Merck Silica Gel 60following established guidelines under positive pressure. Toluene wasfreshly distilled over sodium wire; triethylamine (TEA) was freshlydistilled just prior to use. All other reagents and solvents were usedas purchased, unless stated otherwise.

Procedure for the Synthesis of Cineole Diol from α-Pinene

(following L. A. Popova, V. I. Biba, V. M. Prishchepenko, S. V. Shavyrinand N. G. Kozlov., translated from Zhurnal Obshch Khimii, 1991, Vol. 62,No 7, 1639-1645)

Synthesis of Sobrerol (p-menth-6-ene-2,8-diol)

Sobrerol is prepared according to the standard method by oxidation ofα-pinene with oxygen from the air, giving the pure isomer withequatorial orientation of the substituent at the C₄ and pseudoaxialorientation of the hydroxyl group C₂. Commercially available sobrerolwas sourced from Aldrich as 99% pure p-menth-6-ene-2,8-diol.

Synthesis of Pinol (6,8-epoxy-p-menth-1-ene)

The steam distillation of a flask loaded with sobrerol dissolved in 5%aqueous sulphuric acid gave the crude pinol. The pinol obtained aftersteam distillation was separated from the water in a separating funnelthen dried, and distilled under vacuum by 183-184° C. to give pureproduct.

Synthesis of Cineole Diol (1,8-epoxy-p-menthane-2,6-diol)

Pinol is slowly added with vigorous stirring to a 1:3 ice cooled mixtureof 30% aqueous H₂O₂ and 80% formic acid in such a way that thetemperature did not exceed 40-45° C. The reaction was stirred at roomtemperature overnight and then neutralised with 10% aqueous KOHsolution. Care was taken that the reaction temperature did not exceed50° C. The reaction mixture was allowed to cool to room temperaturebefore the organics were extracted with diethyl ether. The extract wasdried, filtered and the solvent removed to yield the crude product.Re-crystallisation from hot hexane gave fine white crystals of cineolediol in good yield (mp. 120-125° C.). The ¹H and ¹³C NMR spectra matchedthe literature. The total synthesis of cineole diol was repeated severaltimes on 100 g scale.

¹H-NMR (CDCl₃, 400 MHz): δ[ppm]=3.82-3.79 (m, 2H), 3.42 (s, 2H), 2.6-2.5(m, 2H), 1.64 (s, 1H), 1.50, 1.47 (d, 2H), 1.31 (s, 3H), 1.18 (s, 6H).

Procedure for the synthesis of2,2′-((1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diyl)bis(oxy)diethanolfrom cineole diol

1) Synthesis of 2-((tetrahydro-2H-pyran-2-yl)oxy)ethyl4-methylbenzenesulfonate

E. Weber, Liebigs Ann. Chem, 1983, pp 772

2-((tetrahydro-2H-pyran-2-yl)oxy)ethanol (27.22 g, 186.21 mmol) wasdissolved in 120 ml pyridine and the mixture was cooled to −10_° C.4-methylbenzene-1-sulfonyl chloride (37.28 g, 195.50 mmol) was added andthe mixture was allowed to stir for 2 h at −10° C. After stirring for 2h the reaction mixture was poured over ice water (150 ml). Thewater/reaction mixture was extracted with dichloro,ethane (4×150 ml),The combined organic layers were extracted with 10% aqueous CuSO₄solution (5×150 ml) until no colour change (purple to blue) wasobserved. After that the combined organic layers were extracted withsaturated aqueous NH4Cl solution (3×150 ml), saturated aqueous NaClsolution (1×150 ml), dried over MgSO₄, filtered and the solvent removedunder reduced pressure yielding 40.46 g (134.70 mmol, 72%). The crudeproduct was used in the next step without further purification.

¹H-NMR (CDCl₃, 200 MHz): δ[ppm]=7.81, 7.34 (dd, 4H, J=8.0 Hz), 4.62-4.49(m, 1H), 4.17 (t, 2H, J=5.0), 3.95-3.35 (m, 4H), 2.45 (s, 3H), 1.91-1.38(m, 6H)

2) Synthesis of1,3,3-trimethyl-6,7-bis(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)-2-oxabicyclo[2.2.2]octane

P. R. Ashton et al, Eur. J. Org. Chem. 1999, 995-1005

A suspension of finely ground NaOH (6.6 g, 165 mmol) in DMSO (100 ml)was stirred mechanically for 15 min at 50_° C. Cineol diol (3.91 g, 21mmol) was added to the mixture and stirring and heating were maintainedfor 1 h. A solution of 2-((tetrahydro-2H-pyran-2-yl)oxy)ethyl4-methylbenzenesulfonate (18.5 g, 62 mmol) in DMSO (30 ml) was added andthe resulting mixture was heated for 18 h at 80° C. with stirring. Aftercooling down to ambient temperature, the solvent was removed underreduced pressure by trap to trap distillation and the solid residue wastreated with a 1:1 (v/v) mixture of CHCl₃/H₂O (800 ml). The organiclayer was washed withH₂O and dried (MgSO₄). The solvent was removedunder reduced pressure and the residue was purified by columnchromatography (SiO2/EtOAc) to yield1,3,3-trimethyl-6,7-bis(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)-2-oxabicyclo[2.2.2]octane(4.8 g, 10 mmol).

¹H-NMR (CDCl₃, 400 MHz): δ[ppm]=4.71-4.59 (m, 2H), 3.95-3.35 (m, 12H),2.55-2.48 (m, 2H), 1.91-1.39 (m, 17 H), 1.34 (s, 3H), 1.22 (s, 6H)

3) Synthesis of2,2′-((1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diyl)bis(oxy))diethanol

Concentrated aqueous HCl) 0.5 ml) was added to a solution of1,3,3-trimethyl-6,7-bis(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)-2-oxabicyclo[2.2.2]octane.8 g, 10 mmol) in methanol (30 ml). The solution was stirred over nightat ambient temperature after which time no traces of starting materialwere present by TLC (SiO₂/CHCl₃/MeOH, 100:1, (v/v)). The solution wasfiltered, concentrated and the residue was dissolved in CHCl₃ and dried(K₂CO₃) to yield (2.46 g. 9 mmol, 90%) as a yellow oil.

¹H-NMR (CDCl₃, 200 MHz): δ[ppm]=3.85-3.35 (m, 10H), 2.55-2.48 (m, 2H),1.69-1.61 (m, 1H), 1.55-1.43 (m, 2H), 1.31 (s, 3H), 1.18 (s, 6H)

Procedure for the synthesis of2,2′-((1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diyl)bis(oxy))diaceticacid from2,2′-((1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diyl)bis(oxy))diethanol

To a solution of 2,2′4(1,3 ,3-trimethyl-2-oxabicyclo[2.2.2]octane-6,7-diyl)bis(oxy))diethanol (0.5 g, 1.8 mmol) in acetone (10ml) was added 2 ml of Jones Reagent (The Jones Reagent is a solution ofchromium trioxide in diluted sulfuric acid that can be used safely foroxidations of organic substrates in acetone). The reaction mixture wasallowed to stir at ambient temperature for 2 h. After that 5 ml of2-propanol was added. The chromium salts were removed through filtrationand the organic solvents were removed under reduced pressure. The crudeproduct was dissolved in ethyl acetate (10 ml), extracted with 0.01M HClsolution (3×10ml) and dried over MgSO₄. The organic solvent was removedunder reduced pressure and the product (0.52 g, 1.7 mmol, 95%) can beused in the subsequent step without further purification)

¹H-NMR (CDCl₃, 200 MHz): δ[ppm]=6.11-5.35 (br, 2H), 4.32-3.98 (m, 4H),3.87-3.51 (m, 2H), 2.86-1.97 (m, 3H), 1.73-1.43 (m, 2H), 1.41-1.03 (m,9H)

Polymer Methods

Polyesters

Method A: Generic Procedure for the polymerisation of cineole diol withTPA

A flame-dried 50 ml round bottomed flask, equipped with stirring bar,reflux condenser with serum cap, argon inlet (through serum cap), wascharged with 100 mL of dry chloroform, 5.0 g (0.024 mol) ofterephthaloyl chloride, 4.86 g (0.024 mol) of cineole diol (this amountchanged depending on the desired composition) and 5.09 g (0.084 mol) offreshly distilled triethylamine (TEA). The resulting solution wasbrought to reflux and left to react overnight. The mixture was extractedwith chloroform and washed with water three times. The organic factionswere collected, dried and the solvent was removed in vacuo to yield theproduct. This product was then dried in a vacuum oven overnight. Samplesfor ¹H and ¹³C NMR were made up using minimal NMR grade trifluoroaceticacid to first dissolve the polymer then making up the rest of thesolvent with CDCl₃.

Method B: Generic Procedure for the polymerisation of cineole diol, TPAand propane-1,3-diol

A flame-dried 50 mL round bottomed flask, equipped with stirring bar,reflux condenser with serum cap, argon inlet (through serum cap), wascharged with 100 mL of dry chloroform, 5.0 g (0.024 mol) ofterephthaloyl chloride, 1.68 g (0.022 mol) of 1,3-propanediol, 0.486 g(0.0024 mol) of cincolc diol (this amount changed depending on thedesired composition) and 5.09 g (0.084 mol) of freshly distilledtriethylamine (TEA). The resulting solution was brought to reflux andleft to react overnight. The mixture was extracted with chloroform andwashed with water three times. The organic factions were collected,dried and the solvent was removed in vacuo to yield the product. Thisproduct was then dried in a vacuum oven overnight. Samples for ¹H and¹³C NMR were made up using minimal NMR grade trifluoroacetic acid tofirst dissolve the polymer then making up the rest of the solvent withCDCl₃.

Method C: Generic Procedure for the polymerisation of Cineole diol, TPAand ethylene glycol

A flame-dried 50 mL round bottomed flask, equipped with stirring bar,reflux condenser with serum cap, argon inlet (through serum cap), wascharged with 100 mL of dry chloroform, 5.0 g (0.024 mol) ofterephthaloyl chloride, 1.36 g (0.022 mol) of ethylene glycol, 0.486 g(0.0024 mol) of cineole diol (this amount changed depending on thedesired composition) and 5.09 g (0.084 mol) of freshly distilledtricthylaminc (TEA). The resulting solution was brought to reflux andleft to react overnight. The mixture was extracted with chloroform andwashed with water three times. The organic factions were collected,dried and the solvent was removed in vacuo to yield the product. Thisproduct was then dried in a vacuum oven overnight. Samples for ¹H and¹³C NMR were made up using minimal NMR grade trifluoroacetic acid tofirst dissolve the polymer then making up the rest of the solvent withCDCl₃.

Method D: Generic Procedure for the polymerisation of Cineole diol andsuccinyl dichloride

A flame-dried 50 mL round bottomed flask, equipped with stirring bar,reflux condenser with serum cap, argon inlet (through serum cap), wascharged with 10 mL of dry chloroform, 0.41 g (2.6 mmol) of succinyldichloride, 0.5 g (2.6 mmol) of cineole diol and 2.6 g (2.6 mmol) offreshly distilled triethylamine (TEA). The resulting solution wasbrought to reflux and left to react overnight. The mixture was extractedwith chloroform and washed with water three times. The organic factionswere collected, dried and the solvent was removed in vacuo to yield theproduct. This product was then dried in a vacuum oven overnight. Samplesfor ¹H and ¹³C NMR were made up using minimal NMR grade trifluoroaceticacid to first dissolve the polymer then making up the rest of thesolvent with CDCl₃.

Method E: Generic Procedure for the polymerisation of Cineole diol andadipoly dichloride

A flame-dried 150 mL round bottomed flask, equipped with stirring bar,reflux condenser with serum cap, argon inlet (through serum cap), wascharged with 50 mL of dry dichloromethane (DCM) containing 1.83 g (10.0mmol) of cineole diol. 1.83 g (10.0 mmol) of adipoly dichloride wasadded slowly via glass syringe. 2mmol of Pyridine was added over 15minutes and 2.6 g (2.6 mmol) and the mixture was allowed to stirovernight.

The pryridine salt crystals were filtered off and the DCM was removed byrotovap. The resulting solution was brought to reflux and left to reactovernight. . Samples for ¹H and were made up using minimal NMR gradeCDCl₃.

Polyurethanes

Method F: Generic Procedure for the polymerisation of cineole diol andtoluene diisocyanates

An oven dried 50 mL flask was charged with vacuum oven dried 1 g (5.3mmol) of cineole diol. The flask was then placed in an oven at 150° C.until the cineole diol had melted. 2 drops of the catalystdibutyltindilaurate was added. The mixture was then stirred rapidly witha spatula while 0.935 g (5.3 mmol) of 2,4-diisocyanato-1-methylbenzenewas added. The mixture solidified within two minutes giving the product.The product was returned to the oven at 90° C. and left overnight.Samples for ¹H and ¹³C NMR were made up using minimal NMR gradetrifluoroacetic acid to first dissolve the polymer then making up therest of the solvent with CDCl₃.

Method G: Generic Procedure for the polymerisation of cineole diol andMDI

An oven dried 50 mL flask was charged with vacuum oven dried 2 g (10.7mmol) of cineole diol. The flask was then placed in an oven at 150° C.until the cineole diol had melted. 2 drops of the catalystsdibutyltindilaurate was added. The mixture was then stirred rapidly witha spatula while 2.68 g (10.7 mmol) of bis(4-isocyanatophenyl)methane(MDI) was added. The product was returned to the oven at 90° C. and leftovernight. Samples for ¹H were made up using minimal NMR gradedeuterated DMSO

Method H: Generic Procedure for the polymerisation of cineole diol andHDI

An oven dried 50 mL flask was charged with vacuum oven dried 2 g (10.7mmol) of cineole diol. The flask was then placed in an oven at 150° C.until the cineole diol had melted. 2 drops of the catalystsdibutyltindilaurate was added. The mixture was then stirred rapidly witha spatula while 1.8 g (10.7 mmol) of 1,6-diisocyanatohexane was added.The mixture solidified within two minutes giving the product. Theproduct was returned to the oven at 90° C. and left overnight. Samplesfor ¹H were made up using minimal NMR grade in deuterated DMSO

Method I: Generic Procedure for the polymerisation of EG-CD and HDI

An oven dried 50 mL flask was charged with vacuum oven dried 2 g (7.28mmol) of EG capped cineole diol. The flask was then placed in an oven at150° C. until the cineole diol had melted. 2 drops of the catalystsdibutyltindilaurate was added. The mixture was then stirred rapidly witha spatula while 1.22 g (7.28 mmol) of 1,6-diisocyanatohexane was added.The mixture solidified within two minutes giving the product. Theproduct was returned to the oven at 90° C. and left overnight. Samplesfor ¹H were made up in deuterated DMSO

Transesterifcation

Method J: Generic procedure for the reaction of CD with PET

A 25 mL glass ampoule was dried in an oven. The ampoule was fitted witha magnetic stirrer was charged with vacuum oven dried 0.323 g (1.73mmol) cineole diol and 3.00 g PET (Dianite IV=1.2 dg/L), dried to <25ppm water. The ampoule was then placed under vacuum and stirred on amagnetic stirrer for 3 hours. The ampoule was then scaled while undervacuum using a gas torch. The ampoule was then heated to 280° C. in anopen 100mL Parr reactor filled with sand as a heat transfer medium. Theampoule was heated and agitated until the PET and CD was molten. Heatingwas continued until no more of the cineole diol was found to sublime atthe top of the ampoule. The ampoule was then cooled and opened and thecontents were analysed by NMR and GPC.

Method K: Generic Procedure for the reaction of EG-CD with PET

A 25 mL glass ampoule was dried in an oven. The ampoule was fitted witha magnetic stirrer was charged with vacuum oven dried 0.238 g (0.87mmol) cineole diol and 1.5 g PET (Dianite IV=1.2 dg/L), dried to <25 ppmwater. The ampoule was then placed under vacuum and stirred on amagnetic stirrer for 3 hours. The ampoule was then sealed while undervacuum using a gas torch. The ampoule was then heated to 280° C. in anopen 100 mL Parr reactor filled with sand as a heat transfer medium. Theampoule was heated and agitated until the PET and CD was molten. Heatingwas continued until no more of the CD was found to sublime at the top ofthe ampoule. The ampoule was then cooled and opened and the contentswere analysed by NMR and GPC.

Polyamides

Method L: Generic Procedure for the reaction of HAA-CD with HDI to forma polyamide

An oven dried 50 mL flask was charged with vacuum oven dried 2 g (6.62mmol) of Acid capped cineole diol (A-CD). The flask was then placed inan oven at 150° C. until the cineole diol had melted. 2 drops of thecatalysts dibutyltindilaurate was added. The mixture was then stirredrapidly with a spatula while 1.11 g (6.62 mmol) of1,6-diisocyanatohexane was added. The mixture was found to foamindicating the elimination of carbon dioxide to produce the amide. Theproduct was returned to the oven at 90° C. and left overnight. Samplesfor ^(i)H were made up in deuterated DMSO

Characterisation of Polymers

Polymer Samples were Characterised by a Number of Techniques asDescribed below:

NMR—Nuclear Magnetic Resonance

Proton NMR spectra were obtained on Bruker AV400 and Bruker AV200spectrometer, operating at 400 MHz and 200 MHz. All spectra wereobtained at 23° C. unless specified.

Chemical shifts are reported in parts per million (ppm) on the δ scaleand relative to the chloroform peak at 7.26 ppm (¹H) or the TMS peak at0.00 ppm (¹H).

Thermal Analysis:

DSC (Differential Scanning calorimetry) was undertaken on the polymersproduced using the method described above. Samples were weighed intoaluminium pans and the pans placed in a round bottom flask and driedunder vacuum at room temperature overnight. Lids were crimped on the DSCpans and they were then weight to determine the dry weight.

DSC scans were conducted using a Mettler Star SW 9.00 DSC. Thermal scanswere conducted under a nitrogen gas purge using the following method.The pans were heated from 30° C. to 270° C. at 50° C./min, held at 270°C. for lmin and then cooled at 50° C./min to −20° C. (to get samplecontact with the pan), the pans were held at -20° C. for 5mins., thepans were then heated at 10° C./min to 270° C.

Intrinsic Viscosity (IV):

The intrinsic viscosity of the modified PET was measured using ASTMMethod D4603-03: Determining the intrinsic viscosity of PET by GlassCapillary Viscometer. The solvent mixture used was a 1:4 mixture of TFA(triflouro acetic acid) and DCM (dichloro methane). The IV was measuredusing a type 1 Ubedeholle Viscometer. The IV was measured using athermostat controlled water bath at 25° C.

In Table 1 below, the following abbreviations were used: terephthalicacid (TPA), cineole diol (CD) ethylene glycol capped cineole diol(EG-CD), Carboxy ethyl capped-cineole diol (CE-EG), ethylene glycol(E.G.), 1,3-propane glycol (PG), succinic acid (SA), succinoyl chloride(SC), adipoly chloride (AC), 2,4-diisocyanato-1-methylbenzene (TDI),bis(4-isocyanatophenyl)methane (MDI), 1,6-diisocyanatohexane (HDI);pyromellitic dianhydride (PMDA).

Despite the abbreviations used it will be understood that a copolymer ofterephthalic acid and the cyclic compound of Formula (I) where X and Yare H may be formed from the polymerisation of terephthalic aciddichloride and the cyclic diol. Likewise succinyl acid dichloride may beused to form a succinic acid copolymer.

TABLE 1 Modifier (mole % Cincolc Example Polymer diol) Method ¹H NMR  1TPA, CD 50 A 8.17 (m, 4H), 5.1 (s, 1H), 3.92 (s, 1H), 2.84-2.73 (m,(polyester) 2H), 1.96 (s, 1H), 1.77 (s, 1H), 1.53 (m, 3H), 1.31 (m, 9H). 2* TPA, PG 0 A 8.11 (s, 4H), 4.62 (s, 4H), 2.38 (s, 2H). (polyester)  3TPA, CD, PG 5 B 8.12 (m, 4H), 5.20 (s, 5% of 1H), 4.62 (s, 4H),(polyester) 4.20 (s, 5% of 1H), 2.92 (m, 5% of 2H), 2.38 (s, 2H), 1.89(s, 5% of 1H), 1.63 (m, 5% of 3H), 1.41 (s, 5% of 9H).  4 TPA, CD, PG 10B 8.10 (m, 4H), 5.20 (s, 10% of 1H), 4.62 (s, 90% of (polyester) 4H),4.20 (s, 10% of 1H), 2.92 (m, 10% of 2H), 2.38 (s, 90% of 2H), 1.89 (s,10% of 1H), 1.63 (m, 10% of 3H), 1.41 (s, 10% of 9H).  5 TPA, CD, PG 20B 8.06 (m, 4H), 5.20 (s, 20% of 1H), 4.53 (s, 80% of (polyester) 4H),4.20 (s, 20% of 1H), 2.92 (m, 20% of 2H), 2.38 (s, 80% of 2H), 1.89 (s,20% of 1H), 1.63 (m, 20% of 3H), 1.41 (s, 20% of 9H).  6* TPA, E.G. 0 C8.14 (s, 4H), 4.80 (s, 4H) (polyester)  7 TPA, CD, E.G. 5 C 8.12 (m,4H), 5.20 (s, 5% of 1H), 4.62 (s, 95% of (polyester) 4H), 4.20 (s, 5% of1H), 2.92 (m, 5% of 2H), 2.38 (s, 95% of 2H), 1.89 (s, 5% of 1H), 1.63(m, 5% of 3H), 1.41 (s, 5% of 9H).  8 TPA, CD, E.G. 10 C 8.12 (m, 4H),5.20 (s, 10% of 1H), 4.77 (s, 90% of (polyester) 4H), 4.20 (s, 10% of1H), 2.92 (m, 10% of 2H), 2.38 (s, 90% of 2H), 1.89 (s, 10% of 1H), 1.63(m, 10% of 3H), 1.41 (s, 10% of 9H).  9 TPA, CD, E.G. 20 C 8.08 (m, 4H),5.16 (s, 20% of 1H), 4.67 (s, 80% of (polyester) 4H), 4.20 (s, 20% of1H), 2.87 (m, 20% of 2H), 2.38 (s, 80% of 2H), 1.89 (s, 20% of 1H), 1.63(m, 20% of 3H), 1.35 (s, 20% of 9H). 10 CD, SC 50 D 4.88 (s, 2H),4.03-3.83 (m, 2H), 2.70 (m, 6H), (polyester) 2.35 (s, 1H), 1.71-1.09 (m,12H) 11 CD, AC 50 E 4.89-4.79 (m, 2H), 2.76-2.61 (m, 2H), 2.42-2.28 (m,(polyester) 4H), 1.88-1.64 (m, 6H), 1.52-1.02 (m, 12H) 12 CD, TDI 50 F7.09 (m, 3H), 4.90 (m, 2H), 3.84 (s, 1H), 2.72 (s, (polyurethane) 2H),2.27 (m, 4H), 1.72-1.46 (m, 4H), 1.29 (m, 14H) 13 CD, MDI 50 G 9.50 (s),8.56 (s), 7.99 (s), 750-730 (m), (polyurethane) 7.24-7.05 (m), 4.76-4.66(m), 4.11-3.58 (m), 2.93 (s), 2.77 (s), 2.25-2.29 (m), 1.74-1.67 (m),1.57-1.00 (m) 14 CD, HDI 50 H 4.74 (s, 2H), 3.11 (s, 4H), 2.63 (s, 2H),1.77-1.69 (m, (polyurethane) 2H), 1.25 (m, 18H) 15 EG-CD, HDI 50 I5.72-4.52 (br, 2H), 4.37-4.02 (m, 4H), 3.92-3.37 (m, Poly(ether- 6H),3.27-3.01 (m, 4H), 2.62-2.28 (m, 2H), urethane) 1.91-1.01 (m, 20H) 16CE-HDI 50 L 6.99-6.78 (br), 6.42-6.23 (br), 4.34-3.45 (m), (Polyamide)3.37-3.04), 2.84-2.04 (m), 1.84-1.02 (m) 17 CD-PET 5 J 8.31-8.01 (m),4.71 (s), 3.97-3.63 (m), (Polyester) 2.76-2.07 (m), 1.83-1.11 (m) 18CD-PET 10 J 8.31-8.01 (m), 7.41-7.13 (m), 4.71 (s), 4.51 (s),(Polyester) 4.01-3.59 (m), 2.79-2.17 (m), 1.89-1.01 (m) 19 CD-PET 15 J8.31-8.01 (m), 7.40-7.15 (m), 4.72 (s), 4.50 (s), (Polyester) 4.03-3.61(m), 2.81-2.17 (m), 1.89-1.09 (m) 20 CD-PET 20 J 8.32-8.06 (m),7.39-7.13 (m), 4.71 (s), 4.53 (s), (Polyester) 4.02-3.58 (m), 2.77-2.11(m), 1.81-1.07 (m) 21 CD-PET 10 J 8.32-8.06 (m), 7.43-6.98 (m), 4.73(s), 4.51 (s), PDMA 3.66-2.01 (br), 1.71-1.21 (m) (Polyester) 22 CD-PET20 J 8.31-8.05 (m), 7.49-6.91 (m), 6.71-6.61 (m), PDMA 4.73 (s), 4.51(s), 3.16-1.51 (m), 1.31-1.21 (m) (Polyester) 23 CE-CD PET 10 K8.31-8.05 (m), 4.73 (s), 4.51 (s), 3.99-3.51 (m), (Polyester) 2.53-2.48(m), 1.81-1.15 (m) *Comparative exampleThermal Analysis

Thermal analysis, by DSC, of the polymer from Example 1 (Cineolediol-TPA) has shown that the polymer has a glass transition temperatureof approximately 150° C. The Cineole diol-TPA polymer was found not tomelt at 270° C. It is expected that if the molecular weight of theCD-TPA polymer was increased by polycondensation or coupling methodsthat the Tg would also be increased.

Intrinsic Viscosity

The following IV's were measured for the Examples

-   Example 1:IV=0.055 dL/g-   Example 11:IV=0.037 dL/g

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise”, and variations such as“comprises” and “comprising”, will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integers or steps.

The reference in this specification to any prior publication (orinformation derived from it), or to any matter which is known, is not,and should not be taken as an acknowledgment or admission or any form ofsuggestion that that prior publication (or information derived from it)or known matter forms part of the common general knowledge in the fieldof endeavour to which this specification relates.

Many modifications will be apparent to those skilled in the art withoutdeparting from the scope of the present invention.

The invention claimed is:
 1. A compound for use in preparation ofpolymer, the compound being selected from: